QUANTITATIVE RISK ASSESSMENT FOR HIGH PRESSURE GREEN METHANOL

SYNTHESIS FROM GREEN HYDROGEN AND WASTE CARBON DIOXIDE

Ir Dr Zulkifli Abdul Rashid

INPRES, Faculty of Chemical Engineering

Process Safety and Risk reliability Group

UiTM

• Methanol economy proposed firstly by George Olah [1] has identified as the solution forreduction of carbon dioxide emission, boost for renewable energy usage and mass-adoption for hybrid fuel- electric vehicles [2]

• Small scale plant of green methanol (MeOH) production integrated with power andcarbon capture plant was operated firstly by Carbon Recylce Internation (CRI) usinggeothermal power plant [3]. The project by EU called MefCO2 granted CRI to boostproduction of green methanol, thus will see such technology to produce methanol fromgreen hydrogen and waste carbon dioxide put into first place. These highlight theimportance of such mass production of carbon dioxide to methanol production within 10-15 years to come [4].

BACKGROUND

• The progress of lab scale green methanol synthesizes using high pressure shows thatthere are possibilities future plant of carbon dioxide to methanol production will havehigher pressure condition (as high as near 950 bar ),no recycle stream (one pass fullconversion) and design with much reduced reactor volume [5-10].

• Current lab scale experiments absolutely are not focused on the safety aspect in term offatality consequences as lab scale experiments have much smaller size equipment,instead, they are focusing more on design of catalyst and methanol yield.

INTRODUCTION

• However, the question arise on how the effect of chemical release to fatality for largescale production operated at high pressure reactor condition, with recent assessment ofcarbon dioxide to methanol plant only involved for financial and energy [3, 11-13].Furthermore, the pressure condition of reactor only selected at 76- 80 bar. There are noassessment studies for medium to large scale plant operated high pressure conditionexcept one energy study from Tidona et al [7].

• Thus, established method of using quantitative risk assessment has been developed formethanol plant accident scenario [14-17].

INTRODUCTION

• To design green methanol synthesize plant from green hydrogen and waste carbondioxide using simulation design software for mass balance and thermodynamicequilibrium calculation.

• To assess risk of high pressure green methanol using Quantitative Risk Assessment(QRA) via consequence model software for calculation of fatality.

OBJECTIVES

• Abundant of waste carbon dioxide (CO2) from industrialization has increased the globaltemperature, resulting in strong action from scientific community to have a systematicmitigation for CO2.

• Roughly around 40% of waste CO2 emission comes from fossil fuel of natural gas or coalpower plant

• For a coal power plant, the estimation of CO2 emitted is 915 gram per kWh while thegas fired power plant produced 549 gram per kWh and combined cycle gas fired plantemitted roughly 436 gram per kWh

• Malaysia has about 22 combined cycle gas-fired plant and 7 coalfired power plants withcapacity of 20 MW [6]. Therefore, roughly about 12kton per hour of waste CO2 areemitted from this fossil fuel power plant currently and this number will steadily increaseas energy power plant in Malaysia shifts towards coal as the main electricity production[6]

LITERATURE

• To reduce its CO2 emission especially from coal and gas power plant using availableestablished technology

• Utilization of CO2 has gained interest from researchers around the world. CO2 has beenused for urea production process, building material, food and beverages industries, CO2as working fluid for Enhanced Oil Recovery (EOR) and production of carbon to methanol

• Production of carbon to methanol comes from the reaction of hydrogen and waste CO2emissions.

• Meanwhile, hydrogen can produce from surplus electricity of power plant and renewableenergy by electrolysis of water. According to energy consumption analysis by Van Daland Bouallou [9], production of 475kt per year of carbon to methanol needed 12.1 ton/hof H2 using 645.1 MW electricity of water electrolyzer. Therefore, it is a great opportunityfor the growing consumption of renewable energy in Malaysia as there are sufficientamount of hydropower and solar energy to produce hydrogen.

LITERATURE

Review and data compilation of carbon to methanol plant

Design capacity of methanol production, amount of CO2 and hydrogen, reactor

volume and electrolysis capacity using simulation software, HYSYS STAGE

Using quantitative risk assessment by assess the severity and likelihood of the

potential event

List of potential event using hazard identification analysis

Measure severity in term of fatality using fatality analysis

Measure likelihood using the frequency analysis of all potential events

METHODOLOGY

Fatality Assessment based on mixture of chemical release consists of unreacted

H2 and CO2, with the product of reaction – Methanol (MeOH) and Carbon

Monoxide (CO).

Release of the chemical based on volume fraction and mass fraction of individual

chemical in the mixture.

Chemical releases are subjected to three size of leakage – 10mm, 25 mm and

160mm

CO and CO2 are treat as toxicity event while MeOH and H2 are consider both

toxic and flammable event which resulting toxicity, jet fire, flash-fire and vapor

cloud explosion.

Only events that produce red zone threat is consider in this simulation

RESULTS AND DISCUSSION

Fatality Assessment based on mixture of chemical release consists of unreacted

H2 and CO2, with the product of reaction – Methanol (MeOH) and Carbon

Monoxide (CO).

Release of the chemical based on volume fraction and mass fraction of individual

chemical in the mixture.

Chemical releases are subjected to three size of leakage – 10mm, 25 mm and

160mm

CO and CO2 are treat as toxicity event while MeOH and H2 are consider both

toxic and flammable event which resulting toxicity, jet fire, flash-fire and vapor

cloud explosion.

Only events that produce red zone threat is consider in this simulation

RESULTS AND DISCUSSION

15 H2 VCE W 160mm DAY 9

16 CO Toxic SSW 25mm NIGHT 9

17 H2 VCE W 160mm NIGHT 8

18 H2 VCE SSW 160mm NIGHT 8

19 H2 VCE WNW 160mm NIGHT 8

20 CO Toxic W 160mm DAY 8

21 CO Toxic W 25mm DAY 8

22 CO Toxic WNW 10mm DAY 7

23 CO Toxic W 10mm DAY 7

24 CO Toxic WNW 10mm NIGHT 6

25 CO Toxic SSW 10mm DAY 6

26 H2 VCE SSW 25mm NIGHT 6

27 H2 VCE W 25mm NIGHT 6

28 H2 VCE WNW 25mm NIGHT 6

29 H2 VCE SSW 25mm DAY 6

30 H2 VCE W 25mm DAY 6

31 H2 VCE WNW 25mm DAY 6

32 CO Toxic W 10mm NIGHT 6

33 CO Toxic SSW 10mm NIGHT 5

34 H2 Jet fire 160mm NIGHT 4

35 H2 Jet fire 160mm DAY 4

Chemical Event Wind direction Leakage Condition %Fatality

Plant 1 - 76 bar Plant 2 - 442 bar

15 H2 Jet fire 160mm DAY 10

16 H2 Jet fire 160mm NIGHT 10

17 H2 VCE SSW 10mm DAY 8

18 H2 VCE W 10mm DAY 8

19 H2 VCE WNW 10mm DAY 8

20 H2 VCE WNW 10mm NIGHT 7

21 H2 VCE SSW 10mm NIGHT 7

22 H2 VCE W 10mm NIGHT 7

23 CO Toxic WNW 10mm DAY 7

24 CO Toxic WNW 25mm DAY 7

25 CO Toxic WNW 160mm DAY 7

26 H2 Jet fire 25mm NIGHT 6

27 CO Toxic W 10mm DAY 6

28 CO Toxic W 25mm DAY 6

29 CO Toxic W 160mm DAY 6

30 H2 Jet fire 25mm DAY 6

31 CO Toxic SSW 10mm DAY 6

32 CO Toxic SSW 25mm DAY 6

33 CO Toxic SSW 160mm DAY 6

34 MeOH Toxic WNW 25mm DAY 4

35 MeOH Toxic W 25mm DAY 4

Chemical Event Wind direction Leakage Condition %Fatality

1. G. A. Olah, “Beyond oil and gas: The methanol economy,” Angew. Chemie - Int. Ed., vol. 44, no. 18, pp. 2636–2639, 2005.2. C. Mass-adoption and C. Mass-adoption, “Methanol : the Surprising Solution for Pollution , Global Warming and Electric Methanol : the Surprising Solution for

Pollution , Global Warming , and Electric,” pp. 1–21, 2019.3. C. Bergins, K. Tran, E. Koytsoumpa, E. Kakaras, T. Buddenberg, and Ó. Sigurbjörnsson, “Power to Methanol Solutions for Flexible and Sustainable Operations in

Power and Process Industries Mitsubishi Hitachi Power Systems Europe GmbH , Germany * Carbon Recycling International , Iceland,” pp. 1–18, 2015.4. G. C. C. Twitter, G. C. C. Twitter, C. R. International, and E. U. Horizon, “CRI awarded € 1 . 8M EU grant to scale CO2-to-methanol technology,” pp. 1–8, 2019.5. R. Gaikwad, A. Bansode, and A. Urakawa, “High-pressure advantages in stoichiometric hydrogenation of carbon dioxide to methanol,” J. Catal., vol. 343, no.

April, pp. 127–132, 2016.6. A. Bansode and A. Urakawa, “Towards full one-pass conversion of carbon dioxide to methanol and methanol-derived products,” J. Catal., vol. 309, no. January,

pp. 66–70, 2014.7. B. Tidona, C. Koppold, A. Bansode, A. Urakawa, and P. Rudolf Von Rohr, “CO2 hydrogenation to methanol at pressures up to 950 bar,” J. Supercrit. Fluids, vol. 78,

pp. 70–77, 2013.8. A. B. Bansode, “Exploiting high pressure advantages in catalytic hydrogenation of carbon dioxide to methanol,” TDX (Tesis Dr. en Xarxa), 2014.9. R. Gaikwad, “Carbon Dioxide to Methanol : Stoichiometric Catalytic Hydrogenation under High Pressure Conditions,” 2018.10. J. G. van Bennekom et al., “Methanol synthesis beyond chemical equilibrium,” Chem. Eng. Sci., vol. 87, pp. 204–208, 2013.11. É. S. Van-Dal and C. Bouallou, “Design and simulation of a methanol production plant from CO2 hydrogenation,” Journal of Cleaner Production, vol. 57. pp. 38–

45, 2013.12. M. Pérez-Fortes, J. C. Schöneberger, A. Boulamanti, and E. Tzimas, “Methanol synthesis using captured CO2 as raw material: Techno-economic and

environmental assessment,” Appl. Energy, vol. 161, pp. 718–732, 2016.13. E. S. Van-Dal and C. Bouallou, “Design and simulation of a methanol production plant from CO2 hydrogenation,” J. Clean. Prod., vol. 57, no. October, pp. 38–45,

2013.14. L. Lahti, “A guideline for chemical process quantitative risk analysis,” J. Hazard. Mater., vol. 26, no. 1, pp. 101–102, 1991.15. M. J. Assael and K. E. Kakosimos, Fires, Explosions, and Toxic Gas Dispersions - Effects Calculation and Risk Analysis. Boca Raton: CRC Press, 201016. U. de Haag and Ale, Guideline for quantitative risk assessment, 3rd ed. Netherland: CPR, 2005.17. N. Oceanic, A. Administration, and O. Response, “( AREAL LOCATIONS OF HAZARDOUS,” no. November, 2013.

REFERENCES

Acknowledgements

• The authors would like to acknowledge Faculty of Chemical Engineering, UniversitiTeknologi MARA (UiTM) and the Ministry of Education (MOE) for the 600-RMI/FRGS/5/3(0094/2016) grant, for all the funding and support given in establishing this project.

Thanks and Questions

1. The templates given above should be used for the presentation

2. The presentation time is limited to maximum of 20 minutes

3. Number of slides to be limited to facilitate presentation within 20 minutes

4. Font size & color:

• Title of the slides – Tahoma - 28

• Sub-heading – Tahoma - 24

• Content – Tahoma – 22

• Color (titles) – Blue (as indicated)

• Color (content) – Black

5. Question & Answers will be at the end of the session

6. File name should be indicate paper number assigned to the author

Guidelines for Technical Paper & e-Poster Presentation